HistoricoChemical Analysis of Plant Dyestuffs ... - ACS Publications

Chapter 21

Historico—Chemical Analysis of Plant Dyestuffs Used in Textiles from Ancient Israel

Downloaded by STANFORD UNIV GREEN LIBR on June 29, 2012 | http://pubs.acs.org Publication Date: May 5, 1996 | doi: 10.1021/bk-1996-0625.ch021

Zvi C. Koren The Edelstein Center for the Analysis of Ancient Textiles and Related Artifacts, Shenkar College of Textile Technology and Fashion, 12 Anna Frank Street, Ramat-Gan 52526, Israel The history, chemical constitutions, and chromatographic properties of the plant dyestuffs that according to Jewish, Greek, and Roman sources have been used in ancient Israel are discussed. This work is the first published critical historical and chemical analysis of the dyestuffs used in ancient textiles from Israel. The archaeological periods included in this investigation span about a thousand years and primarily include the Hellenistic, Roman, and Byzantine periods, from about the 4th century B.C. to about the 7th century A.D. The primary historical sources relied on for the identification of the dye plants that were used in ancient Israel were the Talmud, related rabbinical literature, and the writings of Greek, Roman, and Jewish historians. Chemical sources that are based on chromatographic and spectrometric analyses of archaeological textile dyeings were also used. The plant dyes investigated belong to a variety of chemical groups, which include flavonoids, carotenoids, safflors and aroylmethanes (all yellows), naphthoquinonoids (browns, reds, oranges), tannins (browns); anthraquinonoids and chalconoids (reds); and indigoids (blues). In addition, a reverse-phase gradient elution high-performance liquid chromatographic (HPLC) method is presented for the separation of dye components from a number of the above classes. Both the historical record and the relevant chemical properties of the dyes presented in this study are necessary for the analysis and proper identification of the colorants used in textiles dyed in ancient Israel. The identification of the colorants used on ancient textiles opens a historical window to the understanding of the processes associated with one of the oldest of chemical technologies - textile dyeing. The analytical inquiries involve chemical detective work to help decipher the identities and sources of the dyestuffs used in antiquity. These investigations of the colorants used by ancient peoples involve a multidisciplinary research that combines history, archaeology, religion, botany, entomology, marine zoology, and microanalytical chemistry. Knowledge of the natural dyes used in different regions in antiquity increases our knowledge of local and international trade and commerce in ancient times. The identification of the textile dyestuffs used can 0097-6156/96/0625-0269$17.50/0 © 1996 American Chemical Society

In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.


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indicate the movement of dyed goods and the transfer of dyeing methods from one geographical area to another. Such an examination of the textiles of past cultures uncovers the development and technological advancement of the "scientific art" of textile dyeing through various archaeological periods. In addition, the study of ancient textiles enhances our understanding of the standard of living, textile art and fashion, and color preferences of ancient peoples. In the religious-historical area, such analyses should help to decipher the mysteries associated with the sources and true colors of the biblical textile dyes - bluish tekhelet, purplish argaman, and reddish tola'at shani. Further, the modern world can also benefit from the instrumental analyses of ancient artifacts. New analytical methods developed for the study of very small archaeological samples may also be applicable to the analyses of modern samples in, for example, industrial quality control, pharmaceutical, environmental, and forensic areas. The historical record is vital for the determination of whether the dyestuffs identified on ancient textiles excavated in Israel were obtained from local sources or imported into this region. Various classical Greek and Roman authors, such as Aristotle, Dioscorides, Vitruvius, Strabo, and Pliny the Elder, have described various aspects associated with textile dyeing as performed during their time. In addition, a number of articles and books have been written in the past few decades on the subject of natural dyes of historical importance. Some of these books include a historical account of various natural dyes (1-4), while others have also included chemical dye constitutions (5-8), and a symposium series has devoted itself to this subject (9). The publications dealing with the historical documentation of the dyes used in antiquity have been based primarily on Babylonian, Greek, Roman, Egyptian and other geopolitical sources. However, very little has been written about the Jewish historical sources that would elucidate the art of textile dyeing as practiced in ancient Israel - that part of the Middle East that is also known as the 'Land of Israel' (Eretz Yisrael in Hebrew) or the 'Holy Land', with its shifting geographical borders over the span of time. A few studies have appeared in Hebrew that discuss some of the historical and botanical aspects of the dyestuffs used in ancient Israel (10-13). This article will investigate those relevant sources written in Hebrew and Aramaic that discuss textile dyeing and dyes and that have been unavailable to the interested reader or researcher who is not versed in those languages. (The translations that appear in this article are the author's.) Further, new chemical research in the field of the analytical separation and spectrometric identification of historically important natural dyes has appeared in the literature and this article will include a new chromatographic scheme for the identification of some of these dyestuffs. As such, this work is the first combined critical historical and chemical analysis of the dyestuffs used in ancient textilesfromIsrael. The historical document that is undoubtedly the most direct witness to the many facets of life in ancient Israel during the Hellenistic, Roman and Byzantine periods is the Talmud (14, 15). The Talmud ("Study" or "Teaching" in Aramaic) formally consists of two parts: the Mishnah (Hebrew for "Repeated Teaching" in an oral manner or "Recitation") and the Gemara ("Teaching" in Aramaic). The Mishnah is a collection of Jewish religious, civil, and agricultural laws that are based on rabbinical interpretations of biblical ordinances and was compiled during the first two centuries of this era. The Gemara consists of rabbinical interpretations of the Mishnah and related commentaries and was compiled between approximately 200 and 500 A.D. Other writings from the talmudic period include the collection of extra-rnishnaic texts known as the Tosephta ("Addition" in Aramaic), which was not formally incorporated into the Mishnah but is contemporaneous with that body of work. While the Mishnah was compiled in Israel and was primarily written in Hebrew, the Gemara is mostly in Aramaic. The current printed format of the Talmud is essentially the same as the first printed version published by Daniel Bomberg in 1520-1523 in Venice. In this arrangement, the Gemara follows the relevant Mishnah. The Talmud contains



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numerous Greek words (written in Hebrew script) that were used by the rabbis ("teachers") of that period. This shows the strong post-Hellenistic Greek influence on the language - especially technical terms - of the Jewish population in Israel during those periods. The Talmud consists of two geographical versions: the Jerusalem Talmud (JT), which is also known as the 'Israeli Talmud' and was produced by the rabbis living in Israel, and the Babylonian Talmud (BT), which is generally the more authoritative and voluminous of the two works and is a product of the rabbis living in Babylonia. The textile craft, in general, and dyeing, in particular, are discussed in various tractates (or volumes) of the Talmud. As is apparent from history, ancient Israel was at the crossroads of various empires and was conquered by them on numerous occasions. This region thus did not live in a vacuum and various types of goods, including textiles, flowed into and out of this strategic region. Hence, the relevant talmudic passages not only reflect on the state of textile dyeing in Israel of the time but also on the level of that craft in neighboring regions. It will, in fact, be observed that many of these talmudic citations closely parallel those of the classical authors that describe the textile art in their regions. The periods to which the term 'ancient Israel' will refer are the Hellenistic (332 B.C. - 63 B.C.), Roman (63 B.C. - 324 A.D.), and Byzantine (324 A.D. - 641 A.D.) Periods. Many dyed textile fragments, which have been dated to these archaeological periods, have been excavated in Israel, and some have undergone chemical analyses (16-24). The quality and diversity of dyeings reached a very high level during the Roman era and analyses of these dyeings have elucidated the techniques used by the ancient dyers of this region. This article will discuss those plants that were described as dyestuffs in the Talmud and were, therefore, cultivated and in use in ancient Israel. Other dye plants that were available in nearby regions, which could have also been imported into this land, are also discussed. Even during talmudic times, products originating from India and from as far away as China found their way to Israel. Some of the more 'exotic' items cited in the Talmud include hinduyin (or, in the variant forms, hindevin, hindoin, hindovin, hindon, hindevon) (25) and dartzona (or dartzina) (26a). Hinduyin are white clothes composed of linen from India (27a) that were worn by the High Priest in the Temple during the afternoonritualon the Day of Atonement; the first part of the name 'hindu' - indicates the geographical origin of the garments. Dartzina is the cinnamon tree and is etymologically derived from the Persian dar-i-cin ("tree that comes from China") (27b). Cotton ("wool of the vine" in talmudic language) was already mentioned in the mishnaic period (28a, 29a) and later (26b, 30a), and silk, which was imported from India (or China), was also known during those early centuries (28b, 31). The three forms of silk that are mentioned in the Talmud are siriqon (26c, 31, 32a, 33a, 34a, 35), shira (26c,d, 28b, 32a, 34a, 36a, 37, 38, 39a,b, 40a), and kalakh (26c, 28b, 29a, 32a), and related etymological variants. Thus, one should not be surprised if one day a dyestuff that was once only available in India or China is found on an archaeological textile excavated in Israel. The dyeing colors obtained from the plant dyestuffs and their known chemical constitutions, including functional group and subgroup affiliations, are also discussed. Finally, a gradient elution method for the separation and identification of dye components from various plant dyestuffs by means of high-performance liquid chromatography (HPLC) is presented. Textile Dyeing - Chemical Considerations In this article, the term 'dyestuff will be used to describe the raw or crude source of the dye, i.e., the plant or part of the plant, and the term 'dye' will refer to the specific



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coloring substance or component of the crude dyestuff. For example, the yellow 'dyestuff weld contains the luteolin and apigenin 'dyes'. A textile may be colored by various means (41). Examples include using different naturally colored fibers, painting a textile with an organic or inorganic pigment, or impregnating the fibers with a soluble form of an inorganic salt or oxide. However, true dyeing with organic dyes yielded the most dramatic and widest range of colors. The process of textile dyeing involves the fixing of a colorant into the textile by physical and/or chemical means so as to produce a direct or indirect bond between the dye and the fiber. As a necessary prelude to the dyeing stage itself, the dye must be present in the aqueous bath in a dissolved form in order to allow the dye molecules to diffuse towards the fibers and penetrate into them. It may have been necessary to control the pH and temperature to maximize the dyeability of the fibers. The wide variety, stability, and beauty of the colors of two thousand year-old dyeings that have survived in the dry climates of Israel attest to the fact that the skillful ancient dyer mastered the necessary dyeing parameters. Natural dyestuffs can be classified according to the following categories: (1) color, (2) source, and (3) chemistry. In the first category, the color of natural dyeings produced were generally red, orange, yellow, brown, and blue. However, many more hues were obtainable by overdyeing with two or more dyestuffs and/or with the formation of a metal-dye complex within the fibers by typically pre-treating the textile fibers with a solution of a metal salt or oxide. The second classification refers to the flora or fauna sources of the dyestuff. Most dyestuffs were vegetal in origin, although certain scale insects and sea snails were also used as dyestuffs (41). The last category is based on the chemical structure or functional class of the dyes, which influences the specific dyeing process used for that class of dye. Consequently, the natural dyes can be chemically classified as either direct, mordant, or vat dyes, which are described in the following sections. The Direct Dyes. These dyes did not require the use of a stabilizing agent in order to fix them into the fibers, though the use of a mordant, as described below, sometimes produced a dyeing that was more fast, i.e., stable. The Mordant Dyes. Many of the natural dyes did not have a strong chemical affinity for the textile fibers. Hence, a mordant (French: "mordre" to bite) or fixing agent was used in antiquity. Metal salts and tannins (polyphenols) served as bridging agents between the fibers and the dye. Mordanting with a metallic ion was accomplished by first impregnating the woolen fibers with an aqueous solution of a metal salt prior to the dyeing stage and subsequently precipitating it as the hydroxide or oxide, or both, within the fibers. The polyvalent-metal salts that were available were "potassium alum", K[A1(S04)]12H20, a source for aluminum ions, and other minerals containing iron, tin, and copper. The resulting precipitated metal-dye complex (42), or lake, consisted of a chelate, where the metal ion could be bonded to two or more dye molecules via ionic and coordinate covalent bonds. This complexation is possible due to the close proximity of the carbonyl oxygen to the phenolic oxygen, i.e., the ahydroxy group. Figure 1 shows the neutral 2:1 complex that 1-hydroxy- and 1,8dihydroxyanthraquinones can form with divalent metal ions, such as copper or zinc (43). Virtually insoluble polymeric complexes can be formed by 1,4- and 1,5dihydroxyanthraquinones (43). The resulting enlarged solid complex that is formed within the fibers, does not easily wash out of the textile and thus the resultant dyeing is relatively fast. The ancient dyers were also undoubtedly aware that the metal mordants served to shade the final color as well. For example, iron chelate complexes with hydroxyanthraquinones dull the colors and can produce chocolate-purple shades with madder dyeings, whereas aluminum complexes produce brighter red shades. These


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colors were found in the Judean Desert textiles excavated at the Cave of Letters (17,18) and at Masada (25), as well as at other archaeological sites in Israel (22, 24). The Vat Dyes. The blue indigotin dye is the most prominent member of this class. This pigment is not soluble in aqueous solutions and in order to solubilize it, a fermentative reduction process was performed in ancient times. First, the insoluble socalled leuco ("white") - or lighter-colored - indigo acid is formed (Figure 2) and, then, this acidic form, in the presence of an alkali from either wood ash, plant ash, lime, or stale urine, reacts to form the soluble salt. Immersion of the textile into the dye solution allows the dissolved dye molecules to penetrate the fibers. Upon removal of the wet dyeing from the bath, air-oxidation will produce the final blue indigotin pigment within the fibers. Successive dyeings will produce darker blue shades and will also yield faster dyeings as the new layer of blue pigment will force the old layer to be driven well within the fibers. Textile Dyeing - Talmudic Considerations Most of the talmudic sources that discuss textile dyeing refer to wool and only two mention dyed linen textiles. One source (44a) is a general reference to linen dyeings, but the other (44b) discusses the dyeing of linen with heret, which is shoe-black that is also used for dyeing leather and wool. This minimal discussion runs parallel to the very few ancient dyed linen textiles that have been excavated in Israel. A commentary by the 11th -12th century French sage Rashi (an acronym for Rabbi Shelomo ben Isaac) on a Talmudic passage (45) states that "it is more difficult for linen to receive the color than for wool." Other textile materials, such as cotton and silk, which were previously mentioned, and hemp or qannabus (28c,d), camel hair (28c, 29a, 32a), and rabbit hair (29a, 32a) were discussed, but not in the context of dyeing. Goat hairs have been mentioned as textile fibers in the Talmud (32a). Textiles containing these fibers have been found at a number of Roman- through Byzantine-period archaeological sites in Israel and one sample was found to be dyed (24). Dyed clothes and accessories were described in the Talmud (26e, 28e, 29b) as, generally, the attire of women (45, 46, 47, 48, 49). An interesting comparison is made between colored garments and fine white linen clothes (50a) : "A man is obligated to gladden his children and household on a festival.... With what does he gladden them? ... Rabbi Judah says: ... (for) men as is fitting for them - with wine; and women, with what? Rabbi Joseph taught: In Babylonia, with colored garments; in Israel, with pressed linen garments." A further parallel is seen from the following two passages: "Thin linen garments from Bet She'an are like colored clothes." (47) "Rabbi Hiya taught: One who wants to beautify his wife should dress her in linen garments." (36b) Though colored clothing was not the 'proper' accouterment for men (51a), nevertheless, the Talmud does mention aritualmantle or prayer shawl - called a tallit worn by men that was completely dyed with the blue (or violet) Tekhelet color (32b, c). In fact, the Bible directed that a thread from the fringes on each corner of a man's garment be dyed Tekhelet (52a) obtained only from a molluskan source (32d). During the talmudic period, and probably prior to it, the dyeing stage of the wool usually preceded the spinning into yarn. The practice of dyeing wool 'in the fleece' can be seen from a number of talmudic passages (26f, 35, 53a,b, 54, 55), as, for example, from the following midrashic statement (54) : "How much did Adam toil before he wore a single robe until he sheared, washed, carded, dyed, spun, wove, and sewed, and thereafter wore (the garment), and I arise in the morning and find all these (garments) before me." In addition, the following citation discusses the different types of work (or activities) that are not to be performed during the Sabbath - the 'day of rest' - and these acts are listed in the following procession (53a): "The main labors



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Figure 1. Neutral 2:1 complex of 1-hydroxy- and 1,8dihydroxyanthraquinones with divalent metals.

(c) Figure 2. Reduction of indigotin (a) to the soluble leuco salt (c) via the leuco indigo acid intermediate (b) and air-oxidation back to the insoluble pigment.



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(prohibited on the Sabbath) are forty less one:... one who shears the wool, washes it, cards it, dyes it, spins it, ..." That dyeing was performed in the fleece has also been indicated by Pliny (2a). Though dyeing could certainly have been performed for private use in and around the home, textile dyeing was also an industry - as inferred from the talmudic reference to bet hatzabai'm ("house of the dyers") (50b, 56). Certain regulations regarding the dye works were discussed: "A man may not open a bakery or a dyehouse underneath his fellow's storehouse" (57-59) undoubtedly because of the odors, smoke, and heat associated with the operations of these businesses. These two industries also had long-term contracts and credits with numerous clients and, hence, if the landlord wanted to terminate the rental contracts with either business, he had to give the occupants a three-year notice instead of the usual twelve months (60, 61a, 62a) Water was an indispensable ingredient in the dye works and the dyer was not permitted to use the water in a public well except for drinking purposes (61b). Dyeing was a specialized profession that was practiced by a tzaba' ("dyer"). Two dyers are mentioned in the Talmud by name: 'Amram the Dyer (30b) and Menahem ben Signai (or Singai) (63). The dyers were probably organized in a crafts guild as can be inferred from the following (61c): "The woolers and the dyers are entitled to say: 'any transaction that will come into the city, we will all be partners in it.'" The dyer wore a piece of dyed wool around his ear so that he would be recognized for that profession (26g, 29c, 64a). The dyer was thus deemed by the Talmud as a skilled professional practicing his craft like many other craftsmen. However, despite the skill of the dyer, the dyeing process was an empirical technology and not without accidents (65). Financial penalties based on legal judgments are discussed for the mishaps described in the following case studies (66): "If one gave wool to a dyer and the vat 'scorched' it, (then the dyer) pays him (the owner) the value of his wool." Dyed wool was always worth more than undyed wool. This was so even if the dyeing yielded an inferior (or "unsightly") or undesirable color: "(If) he dyed it badly, and if the value of the improvement (in the wool as a result of its dyeing) exceeded the (dyer's) outlay, (the owner of the wool) only pays him the outlay; and if the outlay were worth more than the improvement, then he pays him the value of the improvement. (If he requested the dyer) to dye it red, but he dyed it black, or black but he dyed it red, (then) Rabbi Judah says that (as in the previous case, the wool owner only pays him the lower of the two values)." If a different color from the one requested is produced due to the presence of a residue from a previous dyeing in the vat, then, it is up to the dyer to recompense the wool owner the value of his wool (66, 67a). However, if the dyestuffs that were brought to the dyer by the wool owner caused the damage, then the wool owner pays for the costs of dyeing or the extra worth of the dyed wool, whichever is lower. In one rabbi's opinion, if a different color is produced, then the dyer should pay the wool owner the value of the undyed wool plus the extra worth of the dyed wool because the dyer did not clean his vat before dyeing. However, if this change in color was produced unintentionally, then the dyer should not be fined for the extra worth of the dyed wool (67a). Though gloves were used by at least some dyers (68a) their hands were probably nevertheless stained. This is particularly so in the case of blue woad dyeings, as described in the section on woad below. The pre-dyeing stages described by the Talmud, generally involved grinding the raw dyestuff (69) and soaking the plant grounds in water (26f). The Talmud discusses dyestuffs that have been processed, i.e., "soaked" and readied for dyeing and the raw dyestuffs that have not yet been processed: "One who takes out (from his private property to the public domain) materials (dyestuffs) that are soaking, (the minimum quantity of this mixture that is necessary for this transport to be considered as a work activity prohibited on the Sabbath is if there is) enough to dye a (woolen)



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sample to seal a loom shuttle." The dye mixture would be heated in a vat (yora or yura) (26h,i, 53c, 66, 68b) where the dyeing was to be performed and, once completed, the dyed goods would be placed on a reed mat (68b). The Talmud recognized that dyeing was not a very short process, as can be inferred from the debate between the School of Shammai and the School of Hillel. This dispute concerned whether the dyeing of wool may be started on the eve of the Sabbath before its start at sundown, which would necessitate leaving the goods in the dye bath through the Sabbath (53c). It should also be mentioned that at least as early as the biblical period, and certainly later, organic substrates other than textiles, such as leather or animal skins, were also colored or dyed. One of the items that was ordained to be used as part of the cover for the biblical Tabernacle that housed the Tablet with the Ten Commandments was red-dyed ram skins (70). Leather - shoes, sandals, belts, and saddles - was also dyed a black color in talmudic times (26j, 30c, 40b). In addition, the roots of certain plants or trees, such as 'og (sumac), agah, and vered, whose identities are uncertain, were used as "colors for animals." This phrasing is somewhat ambiguous as the term "for animals" can indicate that the plant colorant was used in any one or more of the following processes associated with the animal or its product: (1) marking or branding of the livestock for identification purposes, as indicated by Feliks (12a); (2) tanning of leather; and (3) coloring of leather. Dioscorides remarks that in Mesopotamia they marked livestock and leather with a sumac dyestuff (2b). Nature's Colors: Plant Dyestuffs of the Talmudic Period and Their Chemical Constitutions Textile dyes from the vegetable kingdom were obviously more plentiful and widely used than the colorants available from the animal world. Although almost a thousand different dye sources may have been used at one time (la), a much smaller number of dyestuffs found continuous use due to their good wash- and light-fast properties. Different plant parts were used to produce the appropriate dyestuff. In some plants, the leaves were utilized for extracting the colorant, while in others, only the roots were used. The flowers of a small number of plants were also used. Stems, branches, berries or fruits, tree trunks, bark, or seeds of some plants and trees also found use as dyestuffs. One of the best historical sources for the determination of which dye plants were cultivated in Israel during the talmudic period is the 'botanical chapter' of the JT, chapter 7 of Tractate Shevi'it. This tractate includes a discussion of the agricultural laws that were in effect only in Israel. These laws included the sabbatical - or seventh (shevi'it) - year for the land and its vegetation. In that year, the land was not to be worked and certain restrictions applied to the commerce in crops collected during that year. Hence, any dye plant discussed in the JT to which at least some of the agricultural laws of the sabbatical year applied, automatically indicates that this plant was definitely cultivated within the geographical borders of the 'Land of Israel' as defined by the rabbis of the talmudic period. The plant dyestuffs discussed in this study have either been explicitly mentioned in the Talmud as a dye source or cited as such by other historical sources and could have been used in the Middle East. Tables I, II, and III contain relevant botanical, historical, and dyeing information regarding these plants, which yield yellow/brown, red/orange, and blue dyestuffs, respectively. The dye components from these plants are listed in Tables I—III and their chemical structures are presented in Tables IV-VII according to the chemical functional groups of these colorants. The dye components listed are those that will be obtained after hydrolysis of the dye substances. This is due to the nature of the dyeing process itself, which uses elevated temperatures to produce the dyeings, and to the modern analyses of ancient dyeings, which usually contain an



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acid hydrolysis step for the stripping of the dye from the textile fibers. Thus, the sugar moieties of most of these substances will have dissociated from the dyes following one or both of these procedures. The Colour Index (C.I.) (71) color classification numbers of the plant dyestuffs catalogued in that index are presented in Tables Ι-ΠΙ, and the constitution numbers and chemical structures of the dye components of each dyestuff are given in Tables IV-VH. The parent structures of the colorants in the latter tables are given in Figures 3-11. The colors of wool dyeings produced with these dyestuffs, with or without a complexing mordant that was originally added as a salt of the metal ion, are listed in Tables I—III. The actual final colors are dependent on many factors associated with the dyeing process, such as temperature, age of dyestuff, other additives, pH of soil, season in which plant was picked, etc. Furthermore, the hues listed may be somewhat different for different dyeings with the same dyestuff. The plants are listed in Tables Ι-ΙΠ in alphabetical English order according to a common name of the dyestuff, but other common names are also given. In the sections below, the italicized parenthetical name is the transliterated common Hebrew plant name. Yellow and Brown Dyestuffs. As Table I indicates, most plant dyestuffs produce yellow, beige, and brown colors without the use of a mordant and the most common dyes in these plants are flavonoids and tannins. Flavonoid-based dyes generally yield yellow colors with or without alum, and, by using copper or iron mordants with some plants, greenish dyeings can also be produced. The tannin-rich dyestuffs yield beige or brown dyeings and are virtually unaffected by mordanting with alum. However, ironmordanted tannin dyeings yield the black iron(III) tannate precipitate within the fibers. In general, all iron-mordanted dyeings are darker than ones obtained with copper, which are darker than aluminum-mordanted dyeings. It seems probable that yellow and brown shades were quite prevalent and cheap, though seasonal factors may have influenced the plant to be used. Unfortunately, many of the yellow dyeings were not fast and, though the historical record describes the use of such dyestuffs, only a few archaeological dyeings excavated in Israel show clear indications of having been dyed with a yellow or brown dyestuff. Further, dyeings containing the iron complexes tend to decompose the textile as the iron oxidizes the organic medium and further acts as a catalyst to erode the textile. The borders around some of the holes found on certain textiles show a thinringof brown or black color where iron was used. Other dye components of the yellow-brown family are the anthraquinone emodin, the safflor of Safflower Yellow, the naphthaquinone juglone, the carotenoid crocetin, and the feruloyl (or aroyl) curcumin. Yellow dye sources were quite abundant. The leaves and stems of many plants produce flavones and flavonols. In addition, leaves and branches of certain trees contain tannins, which produce a brown shade. Wool can be dyed directly with aqueous solutions of flavonoids or tannins without prior mordanting. The yellowproducing flavonoids were used as direct dyes without the use of an intermediary. However, certain flavonoids can be further stabilized in the fiber by complexation with a metal mordant via the adjoining carbonyl oxygen and the negative hydroxyl oxygen, as in the case of the related hydroxyanthraquinones described previously. Yellow and brown plant dyes belonging to other chemical classes, such as naphthoquinonoids and carotenoids, have also been used throughout history. Saffron, the stigmas of Crocus sativus L., whose major colorant is crocetin, has been reported for the orange-yellow colors found on the Cave of Letters textiles (17,18). Flavonoidcontaining yellow dyes were undoubtedly used in a number of textiles excavated in Israel; however, the identities of these dyes are still being researched. The tannins served several purposes, depending on the nature of textile color desired. By themselves, they served as a brown dye source. However, they also served as organic mordants for other dyestuffs. In addition, together with an iron salt, they



romana, rimona

vered, varda

fruit rinds rimon

shrub roots florets

flower stigmas

Yellow 7

YeDow 5

Yellow 6

Punica granatum L.

Rosa canina L. or Rosa phoenicia

Carthamus tinctoriusL.

Crocus sativus L.

Rose

Safflower, false saffron, dyer's thistle

Saffron

karkom

qurtam

vered

colorant for animals

dyestuff, ink-making, game

tanning leather, ink-making

korkema, za'afrana fragrance, food color,

dyestuff, haria', food seasoning and qotzah, food coloring, qurtami, qurtema, medicine for diarrhea moriqa, dardera

afatz, afiza milah

Pomegranate

'afatz

insectproduced cysts on oak trees

Brown 6

Quercus infectoria

(none)

Galls, gall nuts, nut galls

unripe eshhar berries of shrub

Yellow 13 Rhamnus palaestinus Boiss.

Reference to the Plant in Jewish Writings Modern Historical Hebrew Hebraic or Uses Name Aramaic Names

Buckthorn berries, Persian berries

Botanical Information Part of Common Botanical Name of SpeciesCI. Natural Color Number Plant English Name Used

Table I (a). Yellow and Brown Plant Dyestuffs of Ancient Israel: Botanical and Historical Information



whole plant and seeds wood of stem and larger (lower) branches

Yellow 2

Young fustic, Cotinus coggygria Scop, Brown 1 (old name: Rhus cotinus L.) Venetian sumac, smoke tree

Reseda luteola L. Weld, dyer's rocket, dyer's weed

green fruit egoz peels

Brown 7

Jugions regia L.

Walnut nkhpah

kurkum

rhizomes

Yellow 3

Curcuma longa L.

Turmeric

•og

leaves

Brown 6

Rhus coriaria L.

(none)

rikhpah

amgoza, egoza

(none)

dyestuff

dyestuff, ink-making

sumqa (or sumaqa) colorant for animals, tanning leather

Reference to the Plant in Jewish Writings Modern Historical Hebraic or Hebrew Uses Aramaic Names Name

Sumac, dyer's sumac, tanner's sumac

Botanical Information Part of Common Botanical Name of SpeciesCI. Natural Color Number Plant English Name Used

Table 1(a). Continued



beige

yellowish

beige

Tannins: Ellagic acid, Gallic acid, others

Pomegranate

2+

green

yellow dull orange yellow

Crocetin (Carotenoid)

Saffron

yellowbrown

yellowish green

greenish yellow yellow

grayish green

greenish yellow

yellow

purplish dark brown, violet

black

greenish

Fe

greenish brown

greenish yellow

2+

Safflower yellow (Safflor)

dull yellow

orangebrown

2+

Safflower

Rose

a

yellowish

beige

beige-yellow dark Emodin yellow (Anthraquinone)

Tannin hydrolysates: Ellagic acid, Gallic acid, others

Kaempferol Kaempferol 7methyl ether Quercetin Rhamnazin Rhamnetin

3+

Main Dye Components ofDyestuffafter Hydrolysis Color of dyeing on mordanted wool Flavonoids Tannins Others no mordant Al Sn Cu

Galls

Buckthorn

Plant Name

Table I (b). Yellow and Brown Plant Dyestuffs of Ancient Israel: Dyeing Properties


In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. 2+

Colors of dyeings are with the fruits of the rose.

Young fustic Fisetin Dihydrofisetin Myricetin

Tannin hydrolysates

brownish orange

yellowish olive green reddish yelloworange

greenish yellow

yellow

Luteolin Apigenin

yellow

Weld

brownish olive

dark brown browner than with AP+

brown

brownish black

Juglone brown (Naphthoquinone )

orange red

Walnut

orange yellow

2+

Curcumin (Feruloyl) greenish yellow

Fe

Turmeric

Gallic acid, others

Fisetin Quercetin

2+

Sumac

3+

Main Dye Components ofDyestuffafter Hydrolysis Color of dyeing on mordanted wool Flavonoids Tannins Others no mordant Al Sn Cu

Plant Name

Table 1(b). Continued



Red 8

Rubia tinctorum L.; other Rubiacaea spp.

Carthamus tinctorius L.Red 26

Chrozophora tinctoria (L.) A. Juss.

Madder

Safflower, dyer's thistle

Turnsole

hazazit

pukh

kofer, henna kufra

alkanet, lashon habar, lashon hapar

qurtam

berries leshishit and/or leaves

orange-red florets

dyestuff

facial make-up

fragrance

shalshushit; gavshushit

dyestuff

haria', dyestuff; qotzah, food seasoning and qurtami, qurtema, food coloring; moriqa, medicine for diarrhea dardera

fresh or dried puah (or fuah)pua, roots puva

plant

Lichen, orchil, cudbear

Red 28

Lawsonia alba Lam. = Lawsonia inermis (alba)

Henna, Egyptian privet

Rocella spp.

roots

leaves

Alkanna tinctoria TauschRed 20 = Anchusa tinctoria Lam.

Reference to the Plant in Jewish Writings C.I. Natural Part of Plant Modern Historical Uses Color Number Used Hebrew NameHebraic or Aramaic Names

Orange 6

Alkanet, alkanna, anchusa

Botanical Information Botanical Name of Common English Species Name

Table II (a). Red and Orange Plant Dyestuffs of Ancient Israel: Botanical and Historical Information



Turnsole

Safflower

Madder

Alizarin, Purpurin, 21 others

Lawsone

Henna

Lichen

Alkannin, Alkannan

Carthamin ( Chalconoid)

Orcein purple, litmus blue

Main Dye Components ofDyestuffafter Hydrolysis AnthraNaphthoOthers quinonoids quinonoids

Alkanet

Plant Name

bluish or reddish

purplish

bright dull red to orange-red to brownish brick-red (stronger, orange "livelier", color red than unmordanted)

dark orange

2+

Cu

dull purple

brownish orange

2+

Sn

bluish red bluish red

burnt orange

violet

3+

no Al mordant

Color of dyeing on mordanted wool

Table II (b). Red and Orange Plant Dyestuffs of Ancient Israel: Dyeing Properties


2+

pink

dark chocolate (or purplish) brown

brownish violet

brown

Fe


Woad

Isatis tinctoria L.

Bluel

Chrozophora tinctoria (L.) A. Juss.

Turnsole fresh leaves, whole plant

isatis

leshishit berries, leaves, stems

hazazit

plant

Red 28

Rocella spp.

nil

leaves

dyestuff

blue (and/or black) eye make-up

dyestuff for the imitation of molluskan Tekhelet

isahs (ovis'tis) dyestuff and variants: satis, sanm, satin, is'tin (or isatin)

shalshushit, gavshushit

pukh, kahal, kohal

kala-ilan

Indigotin, Indirubin

Orcein purple, Litmus blue

Indigotin, Indirubin, Kaempferol (in some species)

Reference to the Plant in Jewish Writings Main Dye Part of Plant Modern Historical Components of Used Hebrew NameHebraic or Uses Dyestuff after Aramaic Names Hydrolysis

Indigofera tinctoria Blue 1

Lichen, orchil, cudbear

Indigo

Botanical Information Botanical Name of C.I. Common Natural Species English Color Name Number

Table III. Blue Plant Dyestuffs of Ancient Israel



Quercetin 3,3',4',5,7-Pentahydroxy

Fisetin 3,3',4', 7-Tetrahydroxy Kaempferol (Indigo Yellow) 3,4 ', 5,7-Tetrahydroxy Kaempferol 7-methyl ether 3,4',5-Trihydroxy-7-methoxy

Flavonols (3-Hydroxyflavones)

3',4', 5,7- Tetrahydroxy

Luteolin

4 ', 5,7- Trihydroxy

Apigenin

Flavones

FLAVONOIDS

Common name Chemical narne^

Subclass

CHEMICAL CLASS

Buckthorn berries: Yellow 13; Others Buckthorn berries: Yellow 13 Buckthorn berries: Yellow 13; Sumac: Brown 6

75650 75670

Young fustic: Brown 1

Weld, Genista: Yellow 2

Weld: Yellow 2

75640

75620

75590

75580

OH

OH

OH

OH

R3

C. I. Plant Source of Dye: Constitution C.I. Natural Color Number Number of Plant Dyestuff Ring A

OH

OH

OH

OH

3

3

OH

OH

OH

OH

OH

OH

OH

OH

OH

Ring A' R > R4'

Continued on next page

OH

OH OCH

OH

OH

OH

Ring Β Ry

OH

5

R

Substituents*

Table IV. Flavonoid and Isoflavonoid Dyes from Plant Dyestuffs of Ancient Israel



Genista: Yellow 2

OH

OH

OH

3

OH

OCH3

OCH

Ring Β Ry R5

OH

OCH3

OH

OH

OH

4

Ring A' R' R3'

Substituents*

b

Refer to the parent structure in Figure 3. Full name of each flavonoid (whether a flavone or a flavonol) and isoflavonoid has the respective "flavone" or "isoflavone" parent molecule name appended; for example, luteolin is 3\4\5,7-tetrahydroxyflavone and genistein is 4',5,7trihydroxyisoflavone.

a

Genistein 4 5,7- Trihydroxy

Isoflavone 75610

Buckthorn berries: Yellow 13

75690 Rhamnetin 3,3 4 5- Tetrahydroxy-7-methoxy

ISOFLAVON01D

OH

Buckthorn berries: Yellow 13

Rhamnazin 75700 3,4',5-Trihydroxy-3\7-dimethoxy OH

*3

Plant Source of Dye: C.I. Constitution C.I. Natural Color Number Number of Plant Dyestuff Ring A

Common name Chemical name**

Subclass

CHEMICAL CLASS

Table IV. Continued



75500 75480

Juglone 5-Hydroxy-

Lawsone 2-Hydroxy-

Henna: Orange 6

2

2

2

OH

3

3

H ι -ÇHCH C=C(CH ) OH

2

3

HistoricoChemical Analysis of Plant Dyestuffs ... - ACS Publications

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